Ultra mild surfactant with good lather

ABSTRACT

This invention comprises a synthetic surfactant composition which provides ultra skin mildness, and excellent lather. This invention is based on an ultra mild surfactant composition comprising: C 8  alkyl glyceryl ether sulfonate C 8  (AGS). The C 8  AGS offers a remarkable combination of desirable properties for mild cleansing formulations.

This is a continuation of application Ser. No. 07/799,916, filed on Nov.26, 1991 now abandoned; which is a continuation of application Ser. No.07/459,100, filed Dec. 29, 1989, now abandoned.

TECHNICAL FIELD

This invention relates to mild surfactants with good lather.

BACKGROUND OF THE INVENTION

This invention relates to mild surfactants and to cleansers comprisingmild synthetic surfactants.

Personal cleansing with mild surface-active cleansing preparations hasbecome a focus of great interest. Many people wash and scrub their skinand hair with various surface-active preparations frequently. Idealcleansers should cleanse gently, causing little or no irritation,without defatting and overdrying after frequent routine use. Mostlathering soaps, shampoos, dishwashing liquids, etc., fall short in thisrespect.

Mild Surfactants

For background on the uses and preparation of mild alkyl glyceryl ethersulfonates see Hulter U.S. Pat. Nos. 2,094,489, issued Sep. 28, 1937;Smith 2,427,576, issued Sep. 16, 1947; Smith 2,427,577, issued Sep. 16,1947; and Mills et al. 2,988,511, issued Jun. 13, 1961, all incorporatedherein by reference. See also Whyte U.S. Pat. Nos. 2,989,547, issuedJun. 20, 1961; Pilcher et al. 2,999,068, issued Sep. 5, 1961; and Whyteet al. 3,024,273, issued Mar. 6, 1962, all incorporated herein byreference. While the prior art discloses the preparation and/or the useof alkyl glyceryl ether sulfonate (AGS) per se (e.g., U.S. Pat. No.3,024,273, supra), many do not even mention C₈ AGS, and none uses a C₈AGS in a personal cleansing example.

Likewise, Tokosh et al. U.S. Pat. No. 4,180,470, issued Dec. 25, 1979,discloses a detergent bar with from 2-6% of sodium alkoxy hydroxypropane sulfonate (AGS) with alkyl chains of from 8 to 22 carbon atoms;but only C₁₀, C₁₄, and C₁₈ AGS are used in the Examples and only atlevels of 4-5%. A small amount of sodium chloride is also required. Thedetergent bar is predominately acyl isethionate. The AGS and salt areused to improve bar wear rate without adversely affecting its latheringcharacteristics. No advantage of using C₈ AGS is suggested and it is notused in a working example.

In an unrelated art, Ishihara et al. U.S. Pat. No. 3,824,102, issuedJul. 16, 1974, discloses C₈ AGS in high speed silver iodobromideemulsion for photographic coating composition. No C₈ AGS purity detailsare disclosed.

A major drawback of most mild synthetic surfactant systems whenformulated for skin or hair cleansing is poor lather performance. Theuse of high sudsing anionic surfactants can yield acceptable lathervolume. Unfortunately, the highest sudsing anionic surfactants are, infact, poor in skin "patch test" mildness. While the moderately mildsodium lauryl glyceryl ether sulfonate (C₁₂ AGS), is relatively good inlather potential, the ultra mild C₁₈ AGS is very poor in latherpotential. It will be appreciated that mildness and lather, makesurfactant selection a delicate balancing act. Thus, it will beappreciated that rather stringent requirements for mild cleansers limitthe choice of surface-active agents and final formulations representsome degree of compromise. Mildness is often obtained at the expense ofeffective cleansing and lathering. Needless to say, an ultra mildsurfactant with good lather potential is hard to find.

OBJECTS OF THE INVENTION

An object of the present invention is to provide an ultra mildsurfactant with acceptable lather potential.

Other objects will become apparent from the detailed description below.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a static diffusion cell diagram which is used to measuresurfactant mildness.

FIG. 2 shows comparative lather volume and mildness results of a C₈ AGSsurfactant solution vs. various other AGS surfactant solutions.

FIG. 3 shows mildness patch test results for various concentrations ofC₈ AGS (Example 1) vs. a Standard (Example 7) mixture of AGS.

SUMMARY OF THE INVENTION

This invention is based on an ultra mild, good lathering, alkyl glycerylether sulfonate surfactant composition comprising at least about 65%C₇₋₉ alkyl glyceryl ether sulfonate (C₈ AGS) and no more than 35% ofhigher alkyl chained AGS.

DETAILED DESCRIPTION OF THE INVENTION

The invention relates to an ultra mild surfactant composition withsurprisingly acceptable lather potential. The C₈ AGS offers a remarkablecombination of desirable properties for mild cleansing formulationswhich have superior skin mildness and acceptable lather benefits. C₈ AGScan be used in shampoos, toilet bars, light duty liquids, or any othersurfactant-based product which comes in contact with the skin.

Commonly assigned Small et al. U.S. Pat. Nos. 4,673,525, issued Jun. 16,1987, and Stiros 4,338,211, issued Jul. 6, 1982, hereby incorporatedherein by reference, disclose personal cleansing products in which theultra mild AGS surfactant of this invention can be used for improvementsof such already mild products.

The preferred cation in the AGS salt is sodium. However, other cationssuch as triethanolammonium (TEA), ammonium, and K, etc., are alsousable.

The percentages, ratios, and parts herein are on a total composition orsurfactant weight basis, unless otherwise specified. All levels andranges herein are approximations unless otherwise specified.

The ultra mild C₈ AGS which has a Relative Skin Barrier DestructionValue (as defined hereinbelow) of less than about 1, and any one with aValue of 1 or greater is excluded. The Relative Skin Barrier DestructionValue is a mildness value based on Standard AGS.

The Standard AGS surfactant has an alkyl carbon chain distribution of58% C₁₂ ; 21% C₁₄ ; 10% C₁₆ ; and 9% C₁₈ (58/21/10/9 C₁₂ /C₁₄ /C₁₆/C₁₈). The Standard has a Relative Skin Barrier Destruction Value of 1by definition. The ultra mild AGS surfactant of this inventionpreferably has a Relative Skin Barrier Destruction Value of less thanabout 0.9 and is preferably a better foamer than the prior art Standard,Example 7, as shown in FIGS. 2 and 3. The ultra mild surfactant of thisinvention comprises alkyl glyceryl ether sulfonate (AGS) which has fromabout 65% to about 100% of an AGS surfactant with an alkyl backbonechain of from about 7 to about 9 carbon atoms, or mixtures thereof. Thealkyl has a total of no more than 10 carbon atoms. AGS is derived from acorresponding ether.

In other words, the present invention is an ultra mild, good foamingsurfactant comprising alkyl glyceryl ether sulfonate (AGS) surfactant.The ultra mild AGS surfactant has a hydrophobic group which contains alinear alkyl chain containing from about 7 to 9 carbon atoms, and whichcan contain methyl or ethyl alkyl branch groups for a total of up toabout 10 carbon atoms, e.g., those derived from ethyl octanol, methyloctanol, and the like.

A preferred ultra mild AGS surfactant of this invention contains no morethan about 35%, preferably less than 30%, and more preferably less than25%, of other AGS with linear alkyl chains of 10 or higher carbon atoms.A preferred ultra mild AGS of this invention has from about 75% to about90% C₈ alkyl chains. A more preferred ultra mild AGS surfactant of thisinvention has at least about 80% AGS surfactant having alkyl chains offrom 7 to 9 straight chain carbon atoms, methyl or ethyl branch chainsup to about 10 carbon atoms, and mixtures thereof. The preferred ultramild AGS surfactant comprises a hydrophobic linear chain containingabout 100% eight carbon atoms and has a Relative Skin BarrierDestruction Value of from about 0 to about 0.9, more preferably fromabout 0.1 to about 0.5.

In Vitro Skin Barrier Destruction Test

The skin barrier destruction test (see test apparatus in FIG. 1) is usedto assess the irritancy potential of surfactants. In this test themilder the surfactant, the lesser the skin barrier 4 is destroyed. Skinbarrier destruction is measured by the relative amount of radio-labeledwater (³ H--H₂ O) which passes from the test solution 3 through the skinepidermis 5 into the physiological buffer contained in the diffusatechamber 6. (This test is also described by T. J. Franz in the J. Invest.Dermatol., 1975, 64, pp. 190-195.)

The skin barrier destruction test utilizes a static diffusion cell 1diagrammed in FIG. 1. Human skin epidermis 5 is placed on the flat areaof the diffusate chamber 6 which is filled with physiological buffer (pH7.4) 11 for collection of the transported radio-labeled water. Thediffusate chamber 6 is either surrounded by a water jacket 12 or placedin an aluminum heating block for temperature control. Temperature canthus be provided by circulating water (outflow 8 and inflow 9) pumpedfrom a water bath at a predetermined temperature. A water-jacketed topis connected to a second circulator/temperature bath. Both the diffusatechamber 6 and the test solution reservoir 2 are maintained at 37° C. AnO-ring joint clamp secures the test solution reservoir 2, sandwichingthe skin epidermis 5 in between it and the diffusate chamber 6.

This test uses cells which have a diffusion area of 0.20 cm². Thediffusate chamber 6 holds approximately 5 ml. The bottom of the chamber6 is flattened to allow spinning of a small magnetic stirring bar 10.The bars 10 are spun by a series of permanent magnets attached toindividual electric motors.

The test solution reservoir 2 holds approximately 1 ml of test solution3. During testing the tops of reservoir 2 are sealed with Parafilm toinhibit evaporation and prevent spillage.

Human abdominal skin is obtained from a local skin bank which procuredand processed the skin for protective freezing and storage as describedby V. P. Perrin (J. Cryosurgery, 1968, 1, 89-99). The sheets of skin aresupplied as 0.012" thickness pieces shipped and maintained on dry iceuntil used. The skin is then thawed by submerging individual packetsunder warm (-95° F.) running water for 3-5 minutes. The skin is then cutinto 3/4"×3/4" squares for mounting onto the diffusion cells.

Test Procedure

The following discussion describes the In Vitro Skin Barrier DestructionTest procedure. Use either 55 or 25 cells per test, 5 replicates pertreatment. This permits testing of either 10 or 4 surfactant solutionsplus a water control. Due to the large variability in percutaneoustransport (site to site and individual to individual), the water controlis a mandatory reference point for each experiment.

Dose test solutions are prepared on a weight/weight basis at 0.5% on atop-loading (±0.01 g) balance. Since each static diffusion cell 1 isdosed with 0.50 ml, a minimum of 3 ml of each test solution 3 should beprepared (5 doses+standard). Each solution is spiked with ³ H--H₂ O toan approximate activity of 1.8 milliCurie/ml dosing solution. Thisinsures a sufficient level of ³ H transport for the sampling interval.

During sample collection, the entire volume of the diffusate chamber 6is emptied through the sampling port 7, rinsed, and refilled with freshbuffer solution 11. Samples are collected at 3, 6, and 24 hours afterinitial dosing. The sample plus rinse is emptied into a scintillationvial and analyzed by liquid scintillation counting.

Standards are included for each sample. One hundred and 200 microlitersamples are placed in individual scintillation vials and brought to 7 mltotal volume with buffer solution. The counts per minute (cpm) fordiffusate samples are converted to equivalent mg water.

All data represent the total quantity of ³ H--H₂ O which penetrate theskin during a 24 hour test duration. Relative Skin Barrier DestructionValues (relative mildness) are calculated for the AGS surfactants ofExamples 1-8 described below in Tables 1 and 2 and illustrated in FIG.2. This is done by dividing the mg of water penetrated for each Exampleby that penetrated for the Standard AGS mixture of Example 7. Thus,numbers greater than 1 indicate greater skin irritation potential thanthe Standard AGS mixture of Example 7. On the other hand, numbers lessthan 1 represent AGS surfactants milder than the Standard.

Relative Foam Volume Potential

In addition to improved and unexpected mildness, the foam volumepotential of the C₈ AGS is important. Thus, a Relative Foam VolumePotential Test is devised to show C₈ AGS's unexpected good foam volumepotential. In short, the Relative Foam Volume Potential of the C₈ AGSsurfactants of the present invention is at least about 75% as good orbetter than the Standard AGS. A quantitative blender foam (latherpotential) volume test is used to measure the Relative Foam VolumePotential of surfactants.

Equipment

1. Specially designed 500 ml graduate cylinder adapted with blenderimpeller. The sharp edge of the impeller blade (2.3 cm) is the trailingedge.

2. Waring Blender Base No. 7011-31BL92 with high/low speed switch.

3. Variac Voltage Regulator. Voltage to blender is adjusted so thatblender disk rotates at 18,000 rpm unloaded (with no cylinder on).

Procedure

1. A 0.5% Solution (dry weight) of the surfactant in tap water is used.

2. Warm and clean cylinder by rinsing it with hot tap water. Drain waterfrom cylinder and check to make sure solution temperature is 95°-105° F.(about 37° C.). (If solution is too cool, it can be warmed gently on ahot plate. Cylinder should be rinsed again if it becomes cool while thisis being done.)

3. Pour 82 ml of solution into cylinder; put cylinder on blender base.Turn blender on for ten seconds, after checking to make sure Variac isset on line.

4. Wait ten seconds and record level of the top of the layer of foam.

5. Repeat procedure with a new solution.

The Relative Foam Volume Potential of the Standard AGS is given thevalue of "1". The C₈ AGS and several other AGS surfactant mixtures andtheir Relative Foam Volume Potential values are shown in FIG. 2 andbelow in Tables 1 amd 2. The C₈ AGS has a Relative Foam Volume PotentialValue of at least 0.75, and preferably from about 1 to about 1.15.

Cleansing Compositions Containing C₈ AGS

In summary, a number of cleansing products can be formulated using theultra mild C₈ AGS as a major or primary surfactant. Small et al. U.S.Pat. Nos. 4,673,525, issued Jun. 16, 1987; and 4,812,253, issued Mar.14, 1989; and Stiros 4,338,211, issued Jul. 6, 1982; all herebyincorporated herein by reference, disclose several personal cleansingproducts. The present C₈ AGS invention can be employed as the sole, aprimary, or co-surfactant, along with one or more ingredients selectedfrom polymeric skin feel aids, moisturizers, fillers, soaps, etc., toprovide improved mildness of the prior art product. The followingpatents disclose or refer to such ingredients and formulations, and arehereby incorporated herein by reference:

    ______________________________________                                        Pat. No.  Issue Date      Inventor(s)                                         ______________________________________                                        3,761,418 9/1973          Parran, Jr.                                         4,234,464 11/1980         Morshauser                                          4,061,602 12/1977         Oberstar et al.                                     4,472,297 9/1984          Bolich et al.                                       4,491,539 1/1985          Hoskins et al.                                      4,540,507 9/1985          Grollier                                            4,673,525 6/1987          Small et al.                                        4,704,224 11/1987         Saud                                                4,812,253 3/1989          Small et al.                                        4,820,447 4/1989          Medcalf et al.                                      ______________________________________                                    

A preferred shampoo composition comprises 1-25%, preferably 3-15%, mildC₈ AGS, 2-25% total foam enhancer and balance water or liquid. Apreferred liquid facial cleanser comprises 1-25%, preferably 5-15%, C₈AGS. A preferred dishwashing liquid comprises from about 3% to about 25%mild C₈ AGS, preferably from about 5% to about 20%, and more preferablyfrom about 10% to about 15% of the ultra mild C₈ AGS. In contrast,liquids made with the Standard AGS alone have a phase separation problemat levels of AGS of over about 0.5%, and with a good co-surfactant theStandard AGS has a phase separation problem at levels of over about 4-5%by weight of the aqueous liquid. C₈ AGS, on the other hand, can be usedat levels up to about 20%, preferably at levels of about 5-18%, byweight of the liquid.

A preferred ultra mild skin cleansing composition is a toilet barcomprising: from 10-80%, preferably from 20-50%, mild C₈ AGS surfactant;from 10-40% moisturizer; from 0.1-5% polymeric skin feel aid, and from5-25% soap. The synthetic surfactant and soap preferably have a ratio offrom 2:1 to 12:1, more preferably the synthetic to soap ratio is from4:1 to 10:1, or from 6:1 to 9:1.

In this respect, limited amounts of other surfactants can be used withthe ultra mild C₈ AGS surfactant of this invention. Numerous examples ofother surfactants are disclosed in the above incorporated by referencepatents. They include alkyl sulfates, soaps, other suitable alkylglyceryl ether sulfonates (AGS), anionic acyl sarcosinates, methyl acyltaurates, N-acyl glutamates, acyl isethionates, alkyl sulfosuccinates,alkyl phosphate esters, ethoxylated alkyl phosphate esters, tridecethsulfates, protein condensates, mixtures of ethoxylated alkyl sulfatesand alkyl amine oxides, betaines, sultaines, and mixtures thereof.Included in the surfactants are the alkyl ether sulfates with 1 to 12ethoxy groups, especially ammonium and sodium lauryl ether sulfates.Alkyl chains for these surfactants are C₁₀ -C₂₂, preferably C₁₀ -C₁₈.Alkyl glycosides and methyl glucose esters are preferred mild nonionicswhich may be mixed with at least one of said mild anionic or amphotericsurfactants in the compositions of this invention. Soaps at levels of1-25%, preferably 5.5-15%, can be included, particularly in barcompositions. The soaps are preferably made in situ via adding a base,e.g., NaOH, to convert free fatty acids in the composition mix.

The other ingredients can be used for the various applications. E.g.,perfumes can be used in formulating the skin cleansing products,generally at a level of from about 0.1% to about 1.5% of thecomposition. Alcohols, hydrotropes, colorants, and fillers such as talcand clay, can also be used. Preservatives, e.g., sodiumethylenediaminetetraacetate (EDTA), generally at a level of less than 1%of the composition, can be incorporated in the cleansing products toprevent microbiological growth. AntibacteriaIs can also be incorporated,Usually at levels up to 1.5%.

Foam Enhancers

The ultra mild surfactant, sodium C₈ glyceryl ether sulfonate, asdefined herein, is ultra mild and is an acceptable foamer. This isdemonstrated in in vitro non-clinical mildness testing and foampotential reports (FIG. 2). While desirable to incorporate into a skincleanser for its mildness properties, this C₈ AGS alone may not provideoptimum lather creaminess for certain executions; thus, foam enhancerscan be added to provide optimum lather creaminess, volume, and/orstability.

The percentage of foam enhancer is defined herein as the Relative Amountby weight of Foam Enhancer to total surfactant unless otherwisespecified. For example, a typical liquid shampoo has about 17% totalsurfactant (e.g., 13% C₈ AGS plus 4% C₁₂ -C₁₃ alkyl polyglycoside). Herethe foam enhancer level is 4% and the total surfactant level is 17%, sothe relative level of the foam enhancer is 4/17 or 23.5% of the totalsurfactant. With the exception of certain salts, the foam enhancers areconsidered part of the total surfactant, for purposes of thiscalculation.

Alkyl polyglycoside detergents are good C₈ AGS foam enhancers. The alkylgroup can vary from about 8 to about 22 and the glycoside units permolecule can vary from about 1.1 to about 5 to provide an appropriatebalance between the hydrophilic and hydrophobic portions of themolecule. Combinations of C₈ -C₁₈, preferably C₁₂ -C₁₆, alkylpolyglycosides with average degrees of glycosidation ranging from about1.1 to about 2.7, preferably from about 1.2 to about 2.5, are preferred.These types can be used at a relative level based on the totalsurfactant of from about 5% to about 60%, preferably from about 20% toabout 50%, and, in some products, from about 22% to about 35% ispreferred.

Amine oxide detergents are good C₈ AGS foam enhancers. Some preferredamine oxides are C₈ -C₁₈, preferably C₁₀ -C₁₆, alkyl dimethyl amineoxides and C₈ -C₁₈, preferably C₁₂ -C₁₆, fatty acyl amidopropyl dimethylamine oxides and mixtures thereof. These types of foam enhancers can beused at a relative level of from about 5% to about 30%, preferably fromabout 8% to about 20% of the total surfactant.

Fatty acid alkanolamides are good C₈ AGS foam enhancers. Some preferredal kanol amides are C₈ -C₁₈, preferably C₁₂ -C₁₆, monoethanolamides,diethanolamides, and monoisopropanolamides and mixtures thereof. Thesetypes of foam enhancers can be used at a relative level of from about10% to about 30%, preferably from about 12% to about 20% of the totalsurfactant.

Betaines are good foam enhancers. Betaines such as C₈ -C₁₈, preferablyC₁₂ -C₁₆, alkyl betaines, e.g., coco betaines or C₈ -C₁₈, preferably C₁₂-C₁₆, acyl amido betaines, e.g., cocoamidopropyl betaine, and mixturesthereof, are preferred. These are used at a relative level of from about10% to about 30%, preferably from about 12% to about 20% of the totalsurfactant.

Water-soluble halide salts can be used as C₈ AGS foam enhancers. Sodium,magnesium, potassium, ammonium, monoethanolamine, diethanolamine, andtriethanolamine (TEA) chloride salts are preferred. These types can beused at a relative level of from about 10% to about 30%, preferably fromabout 12% to about 20% of the total surfactant. MgCl₂ is the preferredsalt.

C₈ AGS "acetone solubles" can be used as foam enhancers. These types offoam enhancers are described in more detail herein and can be used at arelative level of from about 10% to about 40%, preferably from about 15%to about 30%. The principal components of the acetone solubles arepropane-1,2-diol alkyl ether and diglyceryl alkyl ether describedhereinbelow. The alkyl groups correspond to the starting materials.

Certain other surfactants can be used in combination with C₈ AGS toprovide a creamier and more stable lather. One such surfactant is sodiumlauroyl sarcosinate (trade name Hamposyl L, made by Hampshire Chemical).

EXAMPLES

The following examples and methods are illustrative and are not intendedto limit the scope of the invention(s). More details and alternativemethods of making and purifying generic alkyl glyceryl ether sulfonateare disclosed in Mills and Korsi U.S. Pat. No. 2,988,511, issued Jun.13, 1961, incorporated herein by reference. All levels and ranges,temperatures, results etc., used herein are approximations unlessotherwise specified. The following AGS Examples are all made withsaturated straight chain alcohols.

Example 1

Step 1 is the production of alkyl chloroglyceryl ether. One thousandgrams of octanol (C₈ alcohol) are charged to a reaction flask and heatedto 150° F. (65° C). About 4 ml of stannic chloride are added, avoidingexposure to the air outside the reaction flask. (About 2-8 ml of stannicchloride can be added.) The reaction mix is well stirred and maintainedat a temperature of 145°-150° F. (60°-65° C.) while 800 grams ofepichlorohydrin are slowly added at a rate of about one drop per minute.After all the epichlorohydrin has been added the mixture is maintainedat a temperature of 150° F. (65° C.) for 90 minutes more.

Step 2 is the production of alkyl glycidyl ether. Three hundred grams ofalkyl chloroglyceryl ether of Step 1, 183 grams of water and 69 grams ofsodium hydroxide are charged to a well stirred flask and heated to 190°F. (84° C.) for one hour. Stirring is stopped and the mixture allowed tocool to room temperature. The organic layer is separated from theaqueous layer.

Step 3 is sulfonation using as starting reagents 74 grams of alkylglycidyl ether of Step 2, 90 grams of water, 36 grams of sodiummeta-bisulfite and 3 grams of sodium hydroxide are charged to anautoclave. If available. A heel of C₈ AGS from earlier production, about10% of the total reaction mass, is added to the starting reagents.Sodium ethylenediaminetetraacetate (EDTA) is added as a processing aidto chelate metals such as iron. The mixture is well stirred and heateduntil it reaches a temperature of about 360° F. (182° C.) (exothermicheat of reaction will supply part of the heating). The reaction mix isheld at 360° F. (182° C.) for about 25 minutes and then cooled to roomtemperature. The pH is adjusted to about 9 with sodium hydroxide. Thisproduct is 100% C₈ AGS discounting non-AGS materials. It is identifiedas Example 1 in Table 1. See U.S. Pat. No. 2,988,511, supra, fordetailed alternative methods of making and purifying AGS.

Comparative Example 2

Step 1. The production of a 60/40 C₈ -C₁₀ alkyl chloroglyceryl ether isthe-same as in Example 1, except that 352 grams of C₈ -C₁₀ alcohol and262 grams of epichlorohydrin are used. (The alcohol is about 3 partsoctanol to about 2 parts decanol.)

Step 2. The production of alkyl glycidyl ether is the same as in Example1, except that 622 grams of alkyl chloroglycerol ether, 148 grams ofsodium hydroxide and 417 grams of water are used.

Step 3. The sulfonation is the same as in Example 1, except that 57.6grams of alkyl glycidyl ether, 59 grams of water, 24.5 grams of sodiummeta-bisulfite, and 2.4 grams of sodium hydroxide are used. This productis about 60/40 C₈ /C₁₀ AGS as reported in Table 1. Note that themildness value reported in Table 2 is about 1. A 65/35 C₈ /C₁₀ AGS has amildness value of less than 1. See the mildness curve in FIG. 2.

Comparative Example 3

Step 1. The production of a C₁₀ alkyl chloroglyceryl ether is the sameas in Example 1, except that 283 grams of decyl alcohol and 187 grams ofepichlorohydrin are used.

Step 2. The production of alkyl glycidyl ether is the same as in Example2.

Step 3. The sulfonation is the same as in Example 1, except that 300grams of alkyl glycidyl ether, 390 grams of water, 108 grams of sodiummeta-bisulfite, and 11 grams of sodium hydroxide are used. This productis about 100% C₁₀ AGS.

Comparative Example 4

Step 1. The production of a C₁₂ alkyl chloroglyceryl ether is the sameas in Example 1, except that 345 grams of dodecyl alcohol and 193 gramsof epichlorohydrin are used.

Step 2. The production of alkyl glycidyl ether is the same as in Example2.

Step 3. Sulfonation is the same as in Example 1, except that 80 grams ofalkyl glycidyl ether, 94 grams of water, 24.8 grams of sodiummeta-bisulfite, and 2.5 grams of sodium hydroxide are used. This productis about 100% C₁₂ AGS.

Comparative Example 5

A 65/26/6 C₁₂ /C₁₄ /C₁₆ alkyl glycidyl ether is obtained from a Procter& Gamble commercial production. The sulfonation step is the same as inExample 1, except that 36.6 grams of alkyl glycidyl ether, 42.4 grams ofwater, 11 grams of sodium meta-bisulfite, and 1.17 grams of sodiumhydroxide are used. A 65/C₁₂, 26/C₁₄ and 6/C₁₄ AGS mixture is theproduct.

Comparative Examples 6 and 7

The AGS of Example 6 and the AGS Standard Example 7 are commercial cutsobtained from Procter & Gamble. Their alkyl chain distributions are,respectively, 68/25/7 C₁₂ /C₁₄ /C₁₆ and the Standard 58/21/10/9 C₁₂ /C₁₄/C₁₆ /C₁₈ as reported in Tables 1 and 2.

Comparative Example 8

Step 1. The production of the C₁₈ alkyl chloroglyceryl ether is the sameas in Example 1, except that 396 grams of octadecyl alcohol and 260grams of epichlorohydrin are used.

Step 2. The production of alkyl glycidyl ether is the same as in Example1, except that 660 grams of C₁₈ alkyl chloroglyceryl ether, 232 grams ofsodium hydroxide and 926 grams of water are used.

Step 3. The sulfonation is the same as in Example 1, except that 107grams of C₁₈ alkyl glycidyl ether, 134 grams of water, 36.4 grams ofsodium meta-bisulfite, and 3.2 grams of sodium hydroxide are used.

In general, after Step 3, any remaining water phase is separated fromthe AGS surfactant paste. If completion is not good, the paste can bepurified by washing with warm ethyl acetate and/or ethanol.

                  TABLE 1                                                         ______________________________________                                        Summary of Surfactant Chain Lengths Used in Examples 1-8                                                Average                                             AGS Alkyl Chain Length Distribution                                                                       Chain                                             Example C.sub.8                                                                              C.sub.10                                                                             C.sub.12                                                                            C.sub.14                                                                           C.sub.16                                                                           C.sub.18                                                                            Length                            ______________________________________                                        1       100    --     --    --   --   --     8.0                              2        60     40    --    --   --   --     8.8                              3       --     100    --    --   --   --    10.0                              4       --     --     100   --   --   --    12.0                              5       --     --     65    26   6    --    12.4                              6       --     --     68    25   7    --    12.8                              7       --     --     58    21   10    9    13.1                              8       --     --     --    --   --   100   18.0                              ______________________________________                                    

Table 1 sets out the AGS compositions of Examples 1-8. Their RelativeFoam Volumes and Mildness Values are reported in Table 2 and are shownin FIG. 2. All Examples except Example 1 comprise more than 35% C₁₀ -C₁₈AGS. Note that the AGS surfactants of Comparative Examples 2-6 areharsher than the Standard AGS Example 7. But the C₈ AGS, Example 1, ismilder, showing a Relative Skin Barrier Destruction Value is only 0.42.Its Relative Foam Volume Potential Value is 1.10, which is much betterthan the Standard "1". However, a Relative Foam Volume Potential ofabout 0.75 or 0.85 is acceptable so long as the C₈ AGS has a significantmildness advantage over the Standard.

                  TABLE 2                                                         ______________________________________                                        Foam Volumes and Mildness Values for Examples 1-8                                      Avg. Chain   Foam Volume  Mild-                                      Example  Length       (ml) (X/360) ness*                                      ______________________________________                                        1        8.0          395** (1.10) 0.42***                                    2        8.8          440 (1.22)   1.03                                       3        10.0         450 (1.25)   1.62                                       4        12.0         395 (1.10)   1.24                                       5        12.4         410 (1.14)   1.39                                       6        12.8         390 (1.08)   1.56                                       7        13.1         360 (1.00)****                                                                             1.00****                                   8        18.0         100 (0.28)   0.31                                       ______________________________________                                         *Relative Skin Barrier Destruction Value.                                     **Average of two tests on one sample.                                         ***Average of three tests on two samples.                                     ****Reference Point "1" for mildness as well as for Relative Foam Volume      Potential.                                                               

Foam Enhancer-Cylinder Test and Examples 9-15

In some executions, the enhancement of the foam potential of the C₈ AGSsurfactant is desirable. The foam enhancement potential of a potentialenhancer is measured by the Foam Enhancer-Cylinder Test as follows. Tengrams of surfactant solution (with and without foam enhancer) are addedto 108 ml of 100° F. water of the desired hardness. To this is added 2grams of artificial sebum. The mixture is stirred with a magneticstirrer for 15 seconds at high speed, with care being taken not togenerate a foam. The pH is adjusted to 6.5 using NH₄ OH or HCl, asappropriate. The resulting mixed solution is gently added to a 1000 mlgraduated cylinder and stoppered. The cylinder is then mounted on arotating device where it is rotated end-over-end for 20 completerevolutions in approximately 40 seconds. The foam volume in the cylinderis then read immediately, at 1 minute and at 2 minutes. Results arerecorded as is, hence a reading of about 120 ml is indicative of nofoam. In general, triplicate runs are made. In addition, the rotatingapparatus is set up to handle 2 cylinders at a time.

                  TABLE 3                                                         ______________________________________                                        Artificial Sebum Composition                                                  Ingredient        Wt. %                                                       ______________________________________                                        Oleic Acid        19.1                                                        Olive Oil         21.57                                                       Palmitic Acid     5.0                                                         Coconut Oil       19.10                                                       Stearic Acid      2.5                                                         Squalene          6.0                                                         Paraffin Oil (light)                                                                            5.0                                                         Cholesterol       2.5                                                         Lanolin           7.5                                                         Coconut Fatty Acid                                                                              5.8                                                         Dodecane          5.8                                                         Choleth-24        0.03                                                        ______________________________________                                    

Examples 9-15

Examples 9-15, save Example 9, are prepared by adding the foam enhancersto base C₈ AGS at the levels shown in Table 4. The Relative Amount ofFoam Enhancer for Example 9 is 0; for Example 10, 21%; for Example 11,23%; for Example 12, 11%; for Example 13, 15%; and for Example 14, 18%;and for Example 15, 15%. Note that the 2-minute foam volume stability isimproved for all foam enhancers. The levels of C₈ AGS and foam enhancersshown in Table 4 are on a dry weight basis.

                  TABLE 4                                                         ______________________________________                                        Foam Enhancement Data                                                                  Examples                                                             Ingredients                                                                              9      10     11   12    13   14   15                              ______________________________________                                        C.sub.8 AGS (100%)                                                                        17     14     13   17    17   17   17                             Acetone Solubles                                                                         --      3     --   --    --   --   --                              C.sub.12-14 G.sub.1.4 Alkyl                                                              --     --      4   --    --   --   --                              Polyglycosides                                                                Dimethyldodecyl-                                                                         --     --     --    2    --   --   --                              amine Oxide                                                                   Coco-Diethanol-                                                                          --     --     --   --     3   --   --                              amide                                                                         MgCl.sub.2 --     --     --   --    --    3   --                              Cocoamidopropyl                                                                          --     --     --   --    --   --    3                              Betaine                                                                       Water      qs     qs     qs   qs    qs   qs   qs                              Relative % Foam                                                                           0      18     24   11    15   18   15                             Enhancer                                                                      Cylinder Results:                                                             Initial Foam                                                                             445    400    515  360   450  500  540                             Volume (ml)                                                                   2 Min. Foam                                                                              145    390    500  355   440  485  525                             Volume                                                                        ______________________________________                                    

In the Foam Enhancer-Cylinder Test, 10 grams of the solutions are used.While the total surfactant levels in Examples 10-15 range from 17% to20%, they all show improved foam stability or improved foam volume vs.Example 9. In Example 14, the MgCl₂ is not included as a surfactant, soits total surfactant level is 17%. Examples 9, 10, and 11 each have atotal of 17% surfactant. Example 12 has a total of 19% surfactant.Examples 13 and 15 each have a total surfactant level of 20%. Examples12, 13 and 15 maintain their foam stability when their total surfactantlevels are lowered to 17%.

The Acetone Solubles of Example 10 are obtained by stirring about 100grams of C₈ AGS product (43% moisture) with 500 ml of acetone at roomtemperature (23° C.) for about one hour. The resulting insolublecrystals are then filtered off using Whatman filter paper No. 1 on aBuchner funnel. The filtrate containing the acetone solubles is thenconcentrated on a Rotovap at about 45° C., with care being taken toavoid foaming. 50 ml of ethanol is then added and evaporated in order toform an azeotrope and distill off the water. Finally, about 150 ml ofacetone is added to the resulting evaporated product. The resultingsecond crystallization crystals are gravity filtered. The secondfiltrate is then evaporated using the Rotovap. Approximately 4 gm of aclear acetone soluble liquid is isolated. Acetone can be substituted bysolvents of similar polarity. L. R. Snyder, J. Chromatogr., 92, 223(1974).

The "acetone soluble" fraction consists of a number of differentcomponents. The predominant component is propane-1,2-diol octyl ether(Structure I). Other components include, but are not restricted towater, octyl alcohol, C₈ AGS, and diglyceryl octyl ether (Structure II).##STR1## In Table 4, the "Cylinder Results" show that the acetonesolubles are good foam enhancers. About 3 parts are added to about 14parts C₈ AGS for improved foam volume stability, 390 ml vs. 145 ml ofExample 9.

Example 16

In Table 5 is a light duty liquid made with 18% the C₈ AGS of Example 1.A comparable light duty liquid made with the Standard AGS of Example 7has a serious stability problem at ordinary room temperatures. Phaseseparation is the problem for the light duty liquid made with a StandardAGS at an 18% level. Thus, the C₈ AGS light duty liquid of this Exampleprovides a milder product, as well as a more stable product. (C₈ AGS canbe used at levels of from about 5-20% by weight of such liquidproducts.)

                  TABLE 5                                                         ______________________________________                                        Light Duty Liquid                                                             Ingredient          Wt. %                                                     ______________________________________                                        Sodium C.sub.8 AGS  18                                                        Sodium AE.sub.12 S  8                                                         Dimethyldodecylamine oxide                                                                        5                                                         Ethanol             5                                                         Sodium cumene sulfonate                                                                           2                                                         Sodium chloride     2                                                         Miscellaneous (perfumes,                                                                          3                                                         colorants, etc.)                                                              Water               57                                                        Total               100                                                       ______________________________________                                    

The foam enhancer, dimethyldodecylamine oxide, is present at a relativefoam enhancing level of about 16% by weight of the total surfactantsystem (5/31).

Examples 17-20

Toilet bars 17 and 18 of Table 6 are made using a procedure similar tothat disclosed in U.S. Pat. No. 4,673,525, supra, incorporated herein byreference.

                  TABLE 6                                                         ______________________________________                                        Examples of Bars Made with C.sub.8 AGS                                                           Finished Bar (%)                                           Ingredient           Example 17                                                                              Example 18                                     ______________________________________                                        Sodium C.sub.8 AGS   67.25     52.25                                          Stearic Acid         0.90      0.90                                           Coconut Fatty Acid   8.10      8.10                                           Sodium Soap (70/30 Tallow/Coconut)                                                                 9.05      9.05                                           Water                4.00      4.00                                           Polymer JR-400 (Amerchol)                                                                          0.75      0.75                                           Sodium Isethionate (GAF)                                                                           5.00      5.00                                           TiO.sub.2            0.25      0.25                                           Sodium Chloride      4.00      4.00                                           Perfume              0.50      0.50                                           Mayoquest 1545 (EDTA)                                                                              0.20      0.20                                           Cottonseed Triglyceride                                                                            --        15.00                                          Totals               100.00    100.00                                         ______________________________________                                    

Toilet bars Examples 17 and 18 have an unexpected soap-like rinse feelattributed to the C₈ AGS.

Comparative toilet bars, Examples 19 and 20, are the same as the bars ofExamples 17 and 18 except that the prior art Standard Example 7 AGS isused instead of the ultra mild C₈ AGS. These comparative bars, 19 and20, are exemplary of the bars of U.S. Pat. No. 4,673,525, supra. Notethat the AGS Patch Test data shown in FIG. 3 indicate that the C₈ AGSused in Bars 17 and 18 is significantly milder than the Standard AGSused in Bars 19 and 20. Likewise, the C₈ AGS used in Bars 17 and 18 is abetter foamer than the Standard AGS used in Bars 19 and 20 as shown inTable 2 and FIG. 2.

Patch Test Protocol

The purpose of the patch test is to determine the level of primary skinirritation to human test subjects caused by three applications of a testAGS under conditions of occlusion.

Test Procedure: The subjects are 10 to 12 healthy adult volunteersbetween the ages of 18 and 65. Subjects are screened to eliminate thosewith pre-existing dermal allergies or active dermatitis.

The AGS are diluted with distilled water; dilutions are mixed thoroughlyand may be heated slightly to aid in dissolution. Fresh dilutions aremade prior to each patch application. Sufficient diluted test materialsare applied to the patch to saturate the patch surface. Blenderm/Webrilpatches are used for this test.

Four patches are applied to the upper arms and reinforced with strips ofa porous surgical tape of low irritation potential, e.g., MICROPORE® orSCANPOR®. The test is generally conducted according to the followingschedule:

    ______________________________________                                        Friday         First set of patches applied.                                  Saturday       Patches removed* by subject.                                   Monday         Patch sites visually assessed;                                                grades assigned;                                                              second set of patches applied.                                 Tuesday        Patches removed*                                               Wednesday      Patch sites visually assessed;                                                grades assigned;                                                              third set of patches applied.                                  Thursday       Patches removed*                                               Friday         Patch sites visually assessed;                                                grades assigned.                                               ______________________________________                                         *After patch removal, test sites are rinsed using a moistened cloth or        paper towl and patted dry.                                               

Grading: The grading is done by an individual who is familiar with theevaluation of skin reactions and with the 0-4 grading scale (see Table7). If a subject receives a grade two or higher on any test site at anygrading session, that particular site is not re-patched, but the site isgraded to the completion of the test. In these cases, a score of 2.0 orthe actual grade (whichever is higher) is assigned as the final gradeand is used for evaluating the data.

                  TABLE 7                                                         ______________________________________                                        Uniform Laboratory Patch Test Grading Scale                                   0     No apparent cutaneous involvement.                                      1/2   Greater than 0, less than 1.                                            1     Faint but definite erythema, no eruptions or broken                           skin or no erythema but definite dryness; may have                            epidermal fissuring.                                                    1 1/2 Greater than 1, less than 2.                                                  Moderate erythema, may have a few papules or deep                             fissures, moderate-to-severe erythema in the cracks.                    2 1/2 Greater than 2, less than 3.                                                  Severe erythema (beet redness), may have generalized                          papules or moderate-to-severe erythema with slight                            edema (edges well defined by railing).                                  3 1/2 Greater than 3, less than 4.                                                  Generalized vesicles or eschar formations or                                  moderate-to-severe erythema and/or edema extending                            beyond the area of the patch.                                           Typical Examples of-Half-Grad Scores                                          1/2   Faint, barely perceptible erythema or slight dryness                          (glazed appearance).                                                    1 1/2 Well-defined erythema or faint erythema with definite                         dryness, may have epidermal fissuring.                                  2 1/2 Moderate erythema with barely perceptible edema or                            severe etythema not involving a significant portion                           of the patch (halo effect around the edges), may have                         a few papules or moderate-to-severe erythema.                           3 1/2 Moderate-to-severe erythema with moderate edema                               (confined to patch area) or moderate-to-severe                                erythema with isolated eschar formations or vesicles.                   ______________________________________                                    

Results: For each test material, the average of all scores (10-12subjects, 3 grading sessions) is calculated and reported as the averageskin grade. Data can be statistically analyzed if desired; an analysisof variance is performed, followed by a Newman-Keuls test forsignificant differences between pairs of test materials.

Referring to FIG. 3, the C₈ AGS is clearly milder than the Standard AGSat four concentrations, i.e., about 0.04%; 0.08%; 0.5%; and 1%. As shownin FIG. 3, C₈ AGS has a Patch Test Value of less than 0.6 atconcentrations up to about 1%; less than 0.5 at concentrations up toabout 0.8%; less than 0.5 at concentrations up to about 0.5%; and lessthan 0.3 at concentrations up to about 0.2%.

Example 21

A preferred facial cleanser formula using a C₈ AGS similar to that ofExample 1 is set out in Table 8. It has a milder surfactant system thanone made with a comparable amount of Standard AGS.

                  TABLE 8                                                         ______________________________________                                        Ingredient          Solution %                                                ______________________________________                                        Sodium C.sub.8 AGS  5                                                         Lauramide DEA       5                                                         Cocoamidopropyl Betaine                                                                           2.5                                                       Sodium n-Lauroyl Sarcosinate                                                                      2.5                                                       Dowicil 200 (quaternium-15)                                                                       0.2                                                       Perfume             0.05                                                      Water               84.75                                                     Total               100.00%                                                   ______________________________________                                    

Lauramide DEA, the betaine, and the sarcosinate are foam enhancers andare present at relative levels of 331/3%, 162/3%, and 162/3%,respectively, by weight of the total surfactant system. The foamstability for this liquid composition is much better than one in whichthe foam enhancers are replaced with C₈ AGS.

Example 22

Steps 1 and 2 are similar to Example 1. Step 3 is similar to Example 1,except that under sulfonation provides a higher foaming C₈ AGS product.

Under sulfonation in this Example uses 9.11 parts of the alkyl glycidylether of Step 2; 17.75 parts of water; 351 parts of sodiummeta-bisulfate; and 0.38 part of sodium hydroxide. A heel of C₈ AGS fromearlier production, about 10% of the total reaction mass, is added tothe starting reagents. Sodium ethylenediaminetetraacetate (EDTA) isadded as a processing aid to chelate metals such as iron. The mixture iswell stirred and heated until it reaches a temperature of about 360° F.(182° C.) (exothermic heat of reaction will supply part of the heating).The reaction mix is held at 360° F. (182° C.) for about 10-25 minutesand then cooled to room temperature. The pH is adjusted to about 9 withsodium hydroxide. This product is about 70% C₈ AGS and about 30%unsulfonated materials. The principal components of the unsulfonatedmaterials are propane-1,2-diol alkyl ether and diglyceryl alkyl ether,described hereinabove as acetone soluble. The alkyl groups correspond tothe starting materials. Under sulfonation can produce 5-50% unsulfonatedmaterials, preferably 10-40%. The under sulfonated C₈ AGS is a betterfoamer than the fully sulfonated C₈ AGS.

What is claimed is:
 1. An ultra mild skin cleansing compositioncomprising:a) from 10% to 80% by weight of said composition of an ultramild, good foaming surfactant consisting essentially of an alkylglyceryl ether sulfonate surfactant having a hydrophobic group whichcontains an alkyl chain of 8 carbon atoms; and wherein said alkylglyceryl ether sulfonate surfactant has a Relative Skin BarrierDestructive Value of from about 0.1 to about 0.9; b) from 10% to 40% byweight of said composition of a moisturizer; c) from 0.1% to 5% byweight of said composition of a polymeric skin feel aid; and d) from 5%to 25% by weight of said composition of soap.
 2. An ultra mild skincleansing composition according to claim 1 which further comprises from5% to 30% by weight of a foam enhancer based on the weight of surfactantin the composition.
 3. An ultra mild skin cleansing compositionaccording to claim 2 wherein the foam enhancer is selected from thegroup consisting of alkyl polyglycoside detergents, amine oxidedetergents, fatty acid alkanolamides, betaines, water-soluble halidesalts, and C₈ alkyl glyceryl ether sulfonate acetone solubles.
 4. Anultra mild skin cleansing composition according to claim 3 whichcomprises from 20% to 50% by weight of said composition of an ultramild, good foaming surfactant consisting essentially of an alkylglyceryl ether sulfonate surfactant having a hydrophobic group whichcontains an alkyl chain of 8 carbon atoms; and wherein said alkylglyceryl ether sulfonate surfactant has a Relative Skin BarrierDestructive Value of from about 0.1 to about 0.9.
 5. An ultra mild skincleansing composition according to claim 4 wherein said alkyl glycerylether sulfonate surfactant has a Relative Skin Barrier Destructive Valueof from about 0.1 to about 0.5.
 6. An ultra mild skin cleansingcomposition according to claim 5 wherein the weight ratio of said alkylglyceryl ether sulfonate surfactant to soap ranges from 2:1 to 12:1.